Inner shell excitation of CH 3F,CH 3Cl,CH 3Br and CH 3I by 2.5 keV electron impact

Small angle inelastic scattering of 2.5 keV electrons was used to study inner shell excitation in the methyl halides at energy transfers between 50 and 700 eV. Discrete peaks due to the excitation of carbon K, fluorine K, chlorine L, bromine M_{4, 5} and iodine N _{4, 5} electrons were observed. Correlations through the methyl halide series were used to aid in the assignment of features in the carbon K-shell spectra. A comparison of halogen inner-shell excitation structures with the carbon K-shell excitation structure in the same molecule allowed a complete assignment of all spectral features. The assignments proposed involve promotions of inner shell electrons to unoccupied valence and Rydberg orbitals. On the basis of our assignments of the chlorine L- and carbon K-shell electron energy loss spectra of CH ₃Cl we propose an alternate assignment of the previously reported CH ₃Cl chlorine K-shell photoabsorption spectrum.     

Electronic excitations in phosphorus-containing molecules. I. Inner shell electron energy loss spectra of PH3, P(CH3)3, PF3 and PCL3

Electron energy loss Spectroscopy has been used to obtain the inner shell electronic excitation spectra of PH₃, PF₃, PCl₃ and P(CH₃)₃ in the phosphorus L-shell (P 2p, 2s) region as well as the respective ligand K -shells (F 1s, C 1s) and L-shell (Cl 2p and 2s) regions. The spectra were obtained under small momentum transfer conditions so that dipole-allowed transitions dominate. An impact energy of 2.5 ke V was used and inelastically scattered electrons were detected at a typical scattering angle of about 1°. A dipoleforbidden transition of unusual character is observed at 135.11 eV in the P 2p spectrum of PCl₃. Although optically forbidden, as indicated by its absence in a soft X-ray absorption spectrum, the intensity of this transition rises very rapidly with increase in momentum transfer.     

Electronic excitation in phosphorus-containing molecules. II. Inner shell electron energy loss spectra of PF5, OPF3 AND OPCl3

Electron energy loss Spectroscopy has been used to obtain the inner shell excitation spectra of PF₅, OPF₃ and OPCl₃ in the P 2p,2s (L-shell) region as well as in the respective ligand K shell (F 1s, O 1s) and L shell (Cl 2p and 2s) regions. The spectra are compared and contrasted with earlier reported spectra obtained on the trivalent phosphorus compounds (PH₃, PCl₃, PF₃ and P(CH₃)₃). The spectra were obtained using an impact energy of 2.5keV and a scattering angle of about 1°. The spectra reported here are typical of molecules with electronegative ligands in that the discrete portions of the spectra show strong transitions to virtual molecular orbitais. In addition, intense features are observed at or just beyond the ionization edge attributable to transitions to trapped inner well states, while broad features further into the continuum can be ascribed to σ^*(P—L) shape-resonances (L = ligand). This resonance assignment was supported by a comparison with the corresponding spectra for PF₃ and PCl₃.     

Inner shell excitation,valence excitation and core ionization in NF3 studied by electron energy-loss and X-ray photoelectron spectroscopies

Electron energy-loss Spectroscopy (EELS) at impact energies of 2.5–3 keV has been used to obtain the electron excitation spectra for the N 1s (K-shell), F 1s (K-shell) and valence shell regions of NF₃. The inner shell spectra were recorded using small angle scattering (?1° ) while the valence shell spectrum was obtained at zero degree scattering angle. The inner shell excitation spectra show a strongly enhanced 1s→ δ^* type transition and continuum features which are typical for molecules with highly electronegative ligands. One of the peaks in an earlier published photoabsorption study of the N 1s region has been shown to be due to a N₂ impurity. The valence shell electron energy-loss spectrum shows a number of transitions which are considered to be mainly due to valence-valence type transitions, with also some evidence of Rydberg structure.The X-ray photoelectron spectra (XPS) of the N 1s and F 1s electrons along with their associated satellite structures have also been recorded using Al Kα (1486.58 eV) radiation. The vertical ionization potentials for the N 1s and F 1s electrons were found to be 414.36 (10) eV and 693.24 (10) eV, respectively. Both spectra exhibit a rich and different satellite structure. These “shake-up” features in the satellite XPS spectra are compared with continuum features of the inner shell electron energy-loss spectra and also with the valence shell spectrum.     

Relative Cl 2p:P 2s photoionization intensities in transition metal complexes

X-ray photoelectron spectra of the Cl 2p_{$\text{1}\text{2}$, $\text{3}\text{2}$}, P 2s region were obtained for nine transition metal complexes. The Cl:P atom ratios ranged from 1:3 to 3:2 and exhibited a linear relationship with the Cl 2p_{$\text{1}\text{2}$, $\text{3}\text{2}$} : P 2s intensities. Using AlKα radiation, the ratio of the Cl 2p: P 2s photoionization intensities was found to be 2.5: 1.0 with the McPherson ESCA-36 Photoelectron Spectrometer operated in its standard configuration.     

Oscillator strengths for the 2s2, 2p2, 2s3s(1S)-2s2p(1P) transitions of B(II)

Accurate configuration interaction wavefunctions for the 2s²(¹S), 2p²(¹S), 2s3s(¹S) and 2s2p (¹P) states of B(II) are calculated in a single optimized orbital basis of 7s, 6p and 4d Slater-type orbitals. 95, 84, 57 and 90% of the correlation energies, respectively, are realized by these wavefunctions. Oscillator strengths for the three ¹S-¹P transitions are calculated from these and from less accurate wavefunctions in the same orbital basis. The length values obtained from our most accurate wavefunctions, in order of increasing ¹S energy, are 0.9885, 0.202 and 0.007. The degree of accuracy of these oscillator strengths is estimated by noting the convergence to final values as increasing percentages of correlation energies are included in the wavefunctions together with the increasing agreement between length and velocity formulas. The exact theoretical oscillator strength for the resonant line is projected to be 0.985 with an error almost certainly not greater than ±0.015. The theoretical oscillator strengths for the other lines are considered to be 0.21±0.02 and less than 0.007, respectively.     

Derp 3/2-Analogzustand in51V

In an investigation ofT=7/2 analogue states in⁵¹V the⁵⁰Ti(p, γ) excitation curve has been measured for proton bombarding energies 1280–1480 keV and 2340–2660 keV. From the (p, γ) resonances 29 new virtual levels in the region of 9316–9510 keV excitation energy in⁵¹V were determined. The strong resonance atE _p=1 371 keV has been identified as the isobaric analogue state of the⁵¹Ti ground state by determining spin and parity of this resonance to be 3/2^?. There is no evidence for a strong analogue resonance in⁵¹V corresponding to the 1.16 MeV _{p 1/2} state in⁵¹Ti. The γ-decay of the _{p 3/2} analogue state has been studied by measuring branching ratios and angular distributions of primary γ-transitions with a Ge(Li) detector.M1E2 mixing ratios have been determined for these transitions. The total width of the resonance for γ-decay is found to be Γ_γ=1.6±0.4 eV. New bound levels in⁵¹V have been introduced at 3576, 4651 and 4661 keV excitation energy. TheJ ^π values of the 3085, 4770, and 4863 keV states are determined to be 5/2^?, 5/2^?, 3/2^?, respectively. The analogue-antianalogueM1 transition strength is found to be considerably reduced compared to the situation ins-d shell nuclei.     

Vibronic structure of the 3s Rydberg state of the 2-methylallyl radical

Resonance-enhanced multiphoton ionization combined with electronic ground state depletion spectroscopy of jet-cooled 2-methylallyl (C₄H₇) radicals provides vibronic spectra of the 3s and 3p Rydberg states. Analysis of the vibronic structure following one-photon and two-photon excitation of rovibronically cold 2-methylallyl radicals and its isotopologues C₄H₄D₃ and C₄D₇ reveals transitions to more than 30 vibrational levels in the 3s Rydberg state that are identified and reassigned on the basis of predictions from ab initio calculations and results from pulsed-field-ionization zero-kinetic-energy photoelectron spectra obtained with resonant multiphoton excitation via selected intermediate states. Depletion spectroscopy reveals transitions to short-lived 3p Rydberg states that have a large oscillator strength.     

Ion survival probabilities for 3 keV Ar+ scattering from La,Yb, and chemisorbed H2, O2, and H2O on La surfaces

TOF spectra of scattered primary and surface recoiled neutrals and ions for 3 keV Ar⁺ bombardment of clean La and Yb and H₂, O₂, and H₂O saturated La surfaces are presented. The spectra are analyzed in terms of single (SS) and multiple (MS) scattering of the primary ions and surface recoiling (SR) of adsorbate atoms. Measurement of spectra of neutrals + ions and neutrals alone allows determination of scattered ion fractions Y. The Y values for the SS event are high for clean La (37%) and lower for adsorbate covered La (32% for H₂, 13% for O₂, and 8% for H₂O); Yb exhibits a similar behavior, i.e. 16% for clean Yb and 5% for O₂ + H₂O covered Yb. Photon emission accompanying the scattering collision has been observed from clean La and Yb and adsorbate covered La. A preferential inelastic energy loss of 15 ± 3 eV for the SS event has been observed for scattered neutrals as opposed to ions for La and H₂ saturated La at 135°. These results are interpreted within the models for Auger and resonant electronic charge exchange transitions during approach or departure of an ion with a surface and the electron promotions occuring during close atomic encounters where the electron shells are interpenetrating.     

K-shell excitation spectra of CO,N2 and O2

Electron energy loss spectra of CO, N₂ and O₂ have been recorded in the regions of carbon, nitrogen and oxygen K-shell excitation and ionisation. These results are compared to previous energy loss, photoabsorption and theoretical studies of the same spectral regions. Several inconsistencies in the published spectra are clarified in the present work. Comparisons with recent calculations of the K-shell continua of these molecules are presented. Vibrational structure in the K → π * transitions of CO (C 1s) and N₂ (N 1s) has been resolved in high-resolution studies (< 0.1 eV FWHM) of these species.     

The temperature dependence of penning ionization electron energy spectra: He(23S)—ar,N2, NO,O2, N2O,CO2

Using two intense thermal energy He(2³S) sources of different temperatures (≈400 and ≈ 1000 K, resp.) and a transmission-calibrated electron energy analyzer with about 30meV resolution, the dependence of He(2³S) Penning ionization electron spectra on collision energy for the target species Ar, N₂, NO, O₂, N₂O and CO₂ have been studied. The energy shifts of the Penning electron energy distributions and the branching ratios for the population of different electronic states in the molecular ions are determined quantitatively and compared for the two different collision temperatures. These results and the shapes of the observed Penning electron energy distributions are discussed in the light of current models for the Penning procen; the observed temperature dependences are correlated with the nature of the ionized orbitals in cases of only one entrance channel (closed shell targets) and, in addition, to the existence of qualitatively different entrance channels (open shell targets).     

Outers-shell ionization of neon,argon, and krypton by H 2 + and He+ impact (l00 keVto 1000 keV)

The outers-shell ionization of Ne, Ar, and Kr by H ₂ ⁺ and He⁺ impact has been studied in the energy range of 100 keV to 1000keV. The observed structures in the ionization functions are explainable by molecular processes and by direct Coulomb ionization.     

Inner-shell excitation and EXAFS-type phenomena in the chloromethanes

Small angle inelastic scattering of 2.5 keV electrons was used to study the inner-shell excitation of CH₄, CH₃Cl, CH₂Cl₂, CHCl₃, CCl₄ and C₂H₅Cl in the regions of carbon 1s, chlorine 2p and chlorine 2s excitation. Structure observed below the carbon 1s ionization threshold in each molecule is assigned to promotions of a carbon 1s electron to unoccupied valence and Rydberg orbitals. Trends in the distribution of spectral intensities through the series of chloromethane carbon 1s spectra are discussed in terms of the growth of a potential barrier. Broad features are observed in the chlorine 2p continua of CH₂Cl₂, CHCl₃ and CCl₄ and the carbon 1s continuum of CCl₄ which are assigned as the energy loss equivalent of extended X-ray absorption fine structure (EXAFS).     

Polarization in quasielastic (p,2p) scattering on a 4He nucleus at 1 GeV

The polarization of secondary protons from the (p, 2p) reaction induced by 1-GeV protons incident to a ⁴He nucleus was measured in a kinematically complete experiment. By using a two-arm magnetic spectrometer, two secondary protons from this reaction were recorded in coincidence at unequal scattering angles of Θ₁ = 18°?24.21° and Θ₂ = 53.22° over a broad range of the recoil-nucleus momentum K _B between 0 and 150 MeV/c. It was found that the measured polarization of either secondary proton is less than that observed in free elastic proton-proton scattering. The magnitude of this difference is determined by the mean binding energy of s-shell protons rather than by the effective nuclear density. The polarizations measured in inclusive quasielastic and elastic scattering of 1-GeV protons on ⁴He nuclei are presented for scattering angles in the range Θ₁ = 18° ? 24.21°.     

Species formed at cuprite fracture surfaces; observation of O 1s surface core level shift

Surfaces of mineral cuprite prepared by fracture under UHV have been characterised by synchrotron XPS and near-edge X-ray absorption spectroscopy before and after exposure to ambient air. Before exposure of the cuprite, the Cu 2p photoelectron and Cu L_2,3-edge absorption spectra were consistent with Cu^I with very little d⁹ character. Surface-enhanced O 1s spectra from the unexposed mineral revealed a surface species, with binding energy 0.95 ± 0.05 eV below the principal cuprous oxide peak, assigned to under-coordinated oxygen. A second surface species, with binding energy about 1 eV higher than the principal peak, was assigned to either hydroxyl derived from chemisorbed water vapour or surface oxygen dimers produced by restructuring of the cuprite fracture surface. The width of the principal O 1s peak was 0.66 ± 0.02 eV. The observed Cu L₃- and O K-edge absorption spectra were in good agreement with those simulated for the cuprite structure. After exposure of the fracture surface to ambient air, the low binding energy O 1s surface species was barely discernible, the original high binding energy O 1s surface species remained of comparable intensity, new intensity appeared at an even higher (∼1.9 eV) binding energy, and the Cu L_2,3-edge spectrum indicated the presence of Cu^II, consistent with the formation of a thin surface layer of Cu(OH)₂.     

An investigation of the effect of the nearest surroundings on the formation of V Lα emission bands for solid solutions of rare earth orthovanadates—orthophosphates

The V Lα, P Kβ and O Kα X-ray emission spectra for solid solutions YVO₄—YPO₄ and EuVO₄—EuPO₄ have been studied. It is shown that with an increase in concentration of orthophosphate in a substitutional solid solution a hump appears in the low energy part of the V Lα spectrum, corresponding in energy to the P Kβ spectrum. The cluster calculation of the electronic structure of solid solutions YVO₄—YPO₄, carried out by the Extended Hückel method, explains this effect as due to the hybridization of V 3d and P 3p states when [PO₄ ] complexes are introduced into the orthovanadate tetrahedral lattice.     

Experimental study on the 3p size-resonance in thep- wave neutron strength function

Using a silicon filtered fission neutron beam of an energy width of 20 keV around 143 keV we measured the total cross sections for 37 nuclides and elements having mass numbers between 87 and 140 and determined thep-wave strength functions. The 3P-resonance atA=98 shows no splitting into theP _3/2?P _1/2 doublet. The narrow resonance peak and the following broad distribution of thep-strength function (A=103 to 140) can approximately be reproduced by deformed optical model calculations. The spin-orbit term in the optical potential is consistent with the spin orbit force in the shell model. For nuclei around the closed (N=50) neutron shell a shell effect in thep-wave strength function is indicated.     

Pi-mesic decays of A = 4 hypernuclei

Angular distributions and energy spectra for the decay modes _Λ⁴He→π^?p³He, _Λ⁴H → π^?p³H, _Λ⁴H → π^?n³He are calculated and compared with experiment. Final state nuclear interactions have been adjusted to fit the corresponding scattering data. With S-, P- and D-wave interactions we were able to obtain reasonably good agreement with the experimental decay spectra. It is suggested that the _Λ⁴H → π^?n³He decay spectra may be decisive in selecting the right set of p³H complex phase shifts from several possible solutions.     

Embedded structure of silicon monoxide in SiO2 films

The structure of SiO_x (x = 1.94) films has been investigated using both X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The SiO_x films were deposited by vacuum evaporation. XPS spectra show that SiO_1.94 films are composed of silicon suboxides and the SiO₂ matrix. Silicon clusters appeared only negligibly in the films in the XPS spectra. Si₃O⁺ ion species were found in the TOF-SIMS spectra with strong intensity. These results reveal the structure of the films to be silicon monoxide embedded in SiO₂, and this structure most likely exists as a predominant form of Si₃O₄. The existence of Si-Si structures in the SiO₂ matrix will give rise to dense parts in loose glass networks.     

The Compton profile of Bismuth excited below the K absorption edge

A cylindrically symmetric Compton profile spectrometer stimulates resonant Raman scattering at the L₂, L₃, M and N edges in a Bi target when using a ¹⁰⁹Cd γ-ray source with energy 2.50 keV below the K-shell binding energy of Bi. Similarly, an ²⁴¹Am source (E_γ = 59.536 keV) excites a resonance response at the L₃ and M edges of Yb (B.E. = 61.332 keV) but not in Lu (B.E. = 63.314 keV).